WO2007049590A1 - Feuille conductrice d'electricite - Google Patents

Feuille conductrice d'electricite Download PDF

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Publication number
WO2007049590A1
WO2007049590A1 PCT/JP2006/321122 JP2006321122W WO2007049590A1 WO 2007049590 A1 WO2007049590 A1 WO 2007049590A1 JP 2006321122 W JP2006321122 W JP 2006321122W WO 2007049590 A1 WO2007049590 A1 WO 2007049590A1
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WO
WIPO (PCT)
Prior art keywords
carbon fiber
fiber structure
carbon
granular
conductive sheet
Prior art date
Application number
PCT/JP2006/321122
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English (en)
Japanese (ja)
Inventor
Koichi Handa
Subiantoro
Takayuki Tsukada
Tsuyoshi Okubo
Jiayi Shan
Akira Yamauchi
Manabu Nagashima
Original Assignee
Bussan Nanotech Research Institute Inc.
Mitsui & Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bussan Nanotech Research Institute Inc., Mitsui & Co., Ltd. filed Critical Bussan Nanotech Research Institute Inc.
Priority to EP06822102A priority Critical patent/EP1950768A4/fr
Priority to US12/091,404 priority patent/US20090263642A1/en
Publication of WO2007049590A1 publication Critical patent/WO2007049590A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix

Definitions

  • the present invention relates to a novel conductive sheet. More specifically, the present invention relates to a conductive sheet used as a secondary battery separator, a fuel cell separator, a capacitor electrode sheet, an electronic component packaging sheet or the like having excellent conductivity and mechanical strength. .
  • a positive electrode current collector and a positive electrode layer positive electrode active material layer
  • a negative electrode current collector negative electrode current collector
  • the separator conductive sheet
  • the separator is sandwiched between the negative electrode layer (negative electrode active material layer).
  • a polymer electrolyte fuel cell may be configured by stacking single cells each including a polymer solid electrolyte, a gas diffusion electrode, a catalyst, and a separator, for example.
  • the separator is usually provided with a flow path for supplying fuel gas (hydrogen, etc.) and oxidant gas (oxygen, etc.) and discharging the generated moisture (water vapor).
  • high electrical conductivity is required in order to reduce internal resistance.
  • a pair of positive and negative polarizable electrodes (also referred to simply as electrodes) made of activated carbon or the like are opposed to each other through a separator in a solution containing electrolyte ions. It has a structure that allows rapid charge / discharge, is strong against overcharge / discharge, has a long life because it does not involve chemical reactions, can be used in a wide temperature range, and does not contain heavy metals. It has been used for memory knock-up power supplies, etc., but conductive sheets are also used as electrodes for such electric double layer capacitors.
  • conductive sheets are also used as packaging sheets for these electronic components.
  • the conductive sheet may be, for example, various electrode members such as electrostatic It is widely used as various antistatic members in electronic copying machines and electronic printing machines using the cargo latent image development system.
  • a carbonaceous material such as carbon black or graphite powder, or a conductivity imparting agent such as metal powder is blended in an organic polymer material and formed into a sheet shape.
  • a conductivity imparting agent such as metal powder
  • Patent Document 1 contains 5% by weight or more of hollow carbon nanofibers having a diameter of 0.0035 to 0.5 ⁇ m and a length of at least 5 times the diameter in the electrically insulating polymer material.
  • a conductive sheet having a thickness of 10 ⁇ m to 200 ⁇ m is disclosed.
  • the graphite layer constituting the carbon nanofiber usually has a regular, six-membered ring arrangement structure, and has a unique electrical property as well as a chemically, mechanically and thermally stable property. It is a substance with Therefore, if such fine carbon fibers are dispersed and blended in the polymer matrix and the above-mentioned physical properties can be utilized, excellent characteristics can be expected.
  • Patent Document 1 JP-A-3-55709.
  • the present invention has a novel structure of carbon fiber structure that has favorable physical properties as a conductivity-imparting agent, and that can improve electrical characteristics without deteriorating matrix characteristics when added in a small amount.
  • An object is to provide a conductive sheet including a body.
  • the present inventors have intensively studied, and in order to achieve a sufficient improvement in electrical characteristics even if the addition amount is small, the carbon fiber as fine as possible is used. Furthermore, these carbon fibers are firmly bonded to each other without being separated, and are held in a matrix with a sparse structure, and each carbon fiber itself has as few defects as possible. It has been found that it is effective, and the present invention has been achieved.
  • the present invention for solving the above-mentioned problems is a three-dimensional network-like carbon fiber structure in which a carbon fiber force having an outer diameter of 15 to L00 nm is also formed in a polymer matrix,
  • the fiber structure has a granular portion that couples the carbon fibers to each other in a form in which a plurality of the carbon fibers extend, and the granular portions are formed during the growth process of the carbon fibers.
  • It is a conductive sheet characterized in that it contains a carbon fiber structure as a component at a ratio of 0.01 to 30.0% by mass of the whole.
  • the present invention is also characterized in that the carbon fiber structure is measured by Raman spectroscopy.
  • the present invention shows a conductive sheet characterized by being 0.2 or less.
  • the present invention further shows a conductive sheet, wherein the carbon fiber structure is produced using at least two carbon compounds having different decomposition temperatures as a carbon source.
  • the present invention also shows a conductive sheet that is used as an electrode material.
  • the present invention further shows a conductive sheet that is used as an antistatic material.
  • the carbon fiber structure is made of carbon fibers having fine diameters arranged in a three-dimensional network as described above, and the carbon fiber structures are firmly fixed to each other by the granular portions formed in the carbon fiber growth process.
  • the carbon fiber structure In the polymer matrix of the sheet, the carbon fiber structure has a shape in which a plurality of the carbon fibers extend from the granular part.
  • the body has high dispersibility while leaving a sparse structure, and even with a small amount of addition, fine carbon fibers can be evenly spread in the matrix.
  • fine carbon fibers are uniformly distributed throughout the polymer matrix of the sheet.
  • the dispersion is distributed, a good conductive path is formed throughout the matrix, and the conductivity can be improved. Also, in terms of mechanical properties, thermal properties, etc., there is a filler that has a fine carbon fiber strength throughout the matrix. By arranging evenly, the characteristics can be improved.
  • Fig. 1 is an SEM photograph of an intermediate of a carbon fiber structure used in the conductive sheet of the present invention.
  • FIG. 2 is a TEM photograph of an intermediate of a carbon fiber structure used in the conductive sheet of the present invention.
  • FIG. 3 is an SEM photograph of a carbon fiber structure used in the conductive sheet of the present invention.
  • FIG. 4B is a TEM photograph of a carbon fiber structure used in the conductive sheet of the present invention.
  • FIG. 5 is an SEM photograph of a carbon fiber structure used in the conductive sheet of the present invention.
  • FIG. 6 is an X-ray diffraction chart of a carbon fiber structure used in the conductive sheet of the present invention and an intermediate of the carbon fiber structure.
  • FIG. 7 is a Raman spectroscopic analysis chart of a carbon fiber structure used in the conductive sheet of the present invention and an intermediate of the carbon fiber structure.
  • FIG. 8 is a drawing showing a schematic configuration of a production furnace used for producing a carbon fiber structure in an example of the present invention.
  • the conductive sheet of the present invention is characterized by containing a three-dimensional network-like carbon fiber structure having a predetermined structure as described later in a ratio of 0.01 to 30.0 mass% of the whole. Is.
  • the carbon fiber structure used in the present invention also has a carbon fiber force having an outer diameter of 15 to 100 nm as seen in the SEM photograph shown in FIG. 3 or the TEM pictures shown in FIGS. 4A and 4B.
  • the carbon fiber constituting the carbon fiber structure has an outer diameter in the range of 15 to: LOOnm.
  • the outer diameter is less than 15 nm, the carbon fiber has a polygonal cross section as described later.
  • the smaller the diameter of the carbon fiber the greater the number per unit amount, and the longer the length of the carbon fiber in the axial direction and the higher the electrical conductivity, so that the outer diameter exceeding lOOnm can be obtained. It is because it is not suitable as a carbon fiber structure arranged as a modifier or additive in a matrix such as rosin.
  • the outer diameter of the carbon fiber is particularly desirable because it is in the range of 20 to 70 nm.
  • cylindrical graph sheets laminated in the direction perpendicular to the axis are given the ability to return to their original shape even after deformation, ie they are difficult to bend. Therefore, even after the carbon fiber structure is compressed, it is easy to adopt a sparse structure after being arranged in a matrix such as rosin.
  • the fine carbon fiber has an outer diameter that changes along the axial direction. If the outer diameter of the carbon fiber is constant and changes along the axial direction in this way, it is considered that a kind of anchor effect is produced in the carbon fiber in a matrix such as greaves. As a result, the dispersion stability increases.
  • fine carbon fibers having such a predetermined outer diameter exist in a three-dimensional network, and these carbon fibers are grown on the carbon fibers.
  • the granular portions formed in this manner are bonded to each other, and a plurality of the carbon fibers extend from the granular portions.
  • the fine carbon fibers are simply entangled with each other, and they are bonded to each other in a granular part that is not solid, so that they are firmly bonded to each other.
  • the structure can be dispersed and blended in the matrix as a bulky structure without being dispersed as a single carbon fiber.
  • the carbon fibers are bonded to each other by the granular portion formed in the growth process of the carbon fiber.
  • the electrical resistance value measured at a constant compression density indicates that the mere entanglement of fine carbon fibers, or the junction between the fine carbon fibers after the synthesis of the carbon fibers.
  • the value of the structure or the like formed by the substance or its carbide it shows a very low value, and when dispersed and blended in the matrix, a good conductive path can be formed.
  • the granular part is formed in the growth process of carbon fiber as described above, the carbon-carbon bond in the granular part is sufficiently developed, and although it is not clear exactly, sp It seems to include a mixed state of 2 bonds and sp 3 bonds.
  • the granular part and the fiber part are continuous with a structure in which patch-like sheet pieces having carbon atomic force are bonded together, and thereafter After the high temperature heat treatment, as shown in FIGS. 4A and 4B, at least a part of the graphene layer constituting the granular part constitutes the fine carbon fiber extending from the granular part.
  • the graphene layer is continuous.
  • the graphene layer constituting the granular portion as described above is continuous with the graphene layer constituting the fine carbon fiber. Symbolized by the carbon crystal structure bond (at least a part of the bond is formed, thereby forming a strong bond between the granular portion and the fine carbon fiber. It is what.
  • the term “extends carbon fiber force from the granular part” means that the granular part and the carbon fiber are merely apparently formed by other binders (including carbonaceous ones). It is not meant to indicate a connected state, but mainly means a state of being connected by a carbon crystal structural bond as described above!
  • the granular part is formed in the growth process of the carbon fiber, and as a trace thereof, at least one catalyst particle or the catalyst particle is subjected to a subsequent heat treatment inside the granular part.
  • These pores (or catalyst particles) are essentially independent of the hollow portion formed inside each fine carbon fiber extending from the granular portion (note that only a small part is incidental) Some of them are connected to the hollow part;).
  • the number of catalyst particles or pores is not particularly limited, but is about 1 to about LOOO, more preferably about 3 to 500 per granular part. By forming the granular portion in the presence of such a number of catalyst particles, it is possible to obtain a granular portion having a desired size as described later.
  • each catalyst particle or pore present in the granular part is, for example, 1 to: LOOnm, more preferably 2 to 40 nm, still more preferably 3 to 15 nm. .
  • the particle diameter of the granular portion is larger than the outer diameter of the fine carbon fiber as shown in FIG.
  • the outer diameter of the fine carbon fiber is 1.3 to 250 times, more preferably 1.5 to: LOO times, and further preferably 2.0 to 25 times.
  • the said value is an average value. In this way, if the particle size of the granular part, which is the bonding point between the carbon fibers, is sufficiently large such that the outer diameter of the fine carbon fiber is 1.3 times or more, it is higher than the carbon fiber extending from the granular part.
  • the fibrous properties of the carbon fiber structure may be impaired. For example, into the various matrices. This is not desirable because it may not be suitable as an additive or compounding agent.
  • the “particle size of the granular part” in the present specification is a value measured by regarding the granular part which is a bonding point between carbon fibers as one particle.
  • the specific particle size of the granular portion is a force that depends on the size of the carbon fiber structure and the outer diameter of the fine carbon fiber in the carbon fiber structure.
  • the average value is 20 to 5000 nm. It is preferably 25 to 2000 nm, more preferably about 30 to 500 nm.
  • the granular portion is formed in the carbon fiber growth process as described above, it has a relatively spherical shape, and the circularity is 0.2 on average.
  • the granular portion is formed in the carbon fiber growth process as described above.
  • a joint between fine carbon fibers is formed at the carbonaceous material after the carbon fiber is synthesized.
  • the bonding between the carbon fibers in the granular portion is very strong compared to a structure or the like attached by the carbide, and the carbon fiber breaks in the carbon fiber structure. Even below, this granular part (joint part) is kept stable.
  • the carbon fiber structure is dispersed in a liquid medium, and an ultrasonic wave with a predetermined output and a predetermined frequency is applied to the carbon fiber structure, so that the average length of the carbon fibers is almost halved.
  • the change rate of the average particle diameter of the granular part is less than 10%, more preferably less than 5%, and the granular part, that is, the bonded part of the fibers is stably held. It is what.
  • the carbon fiber structure used in the present invention desirably has an area-based circle-equivalent mean diameter of about 50-100 ⁇ m, more preferably about 60-90 ⁇ m.
  • the area-based circle-equivalent mean diameter means that the outer shape of the carbon fiber structure is photographed using an electron microscope or the like, and the contour of each carbon fiber structure is represented by appropriate image analysis software in this photographed image. For example, using WinRoof (trade name, manufactured by Mitani Corporation), the area within the contour is obtained, the equivalent circle diameter of each fiber structure is calculated, and this is averaged.
  • WinRoof trade name, manufactured by Mitani Corporation
  • the electrical conductivity may not be sufficiently exhibited. If it exceeds 100 m, for example, when blended into a matrix by kneading or the like, a large increase in viscosity occurs, making it difficult to mix and disperse or to deteriorate moldability.
  • the carbon fiber structure according to the present invention includes a carbon fiber structure according to the present invention in which carbon fibers existing in a three-dimensional network are bonded to each other in a granular portion, Participation force
  • the carbon fiber has a plurality of extending shapes.
  • a single carbon fiber structure has a plurality of granular parts that combine the carbon fibers to form a three-dimensional network.
  • the average distance between adjacent granular portions is, for example, 0.5 / ⁇ ⁇ to 300 m, more preferably 0.5 to LOO m, and more preferably about 1 to 50 m.
  • the distance between the adjacent granular parts is a distance measured from the central part of one granular body to the central part of the granular part adjacent thereto. If the average distance between the granular materials is less than 0., the carbon fiber does not sufficiently develop into a three-dimensional network. For example, when dispersed in a matrix, a good conductive path is obtained. On the other hand, if the average distance exceeds 300 / zm, it becomes a factor to increase viscosity when dispersed in the matrix, and the matrix of the carbon fiber structure This is because the dispersibility of the ink may be reduced.
  • the carbon fibers existing in a three-dimensional network are bonded to each other in the granular part, and the carbon part is described above.
  • the carbon fiber has a shape in which a plurality of carbon fibers are extended, and thus the structure has a bulky structure in which carbon fibers are sparsely present.
  • the bulk density is 0.0001 to 0.00. It is desirable that it is 05 g / cm 3 , more preferably 0.001-0.02 g / cm 3 . This is because if the bulk density exceeds 0.05 gZcm 3 , it becomes difficult to improve the physical properties of the matrix such as rosin by adding a small amount.
  • the carbon fiber structure according to the present invention is a carbon fiber present in a three-dimensional network form.
  • the electrical characteristics of the structure itself are very excellent.
  • the powder resistance value measured at a constant compression density of 0.8 g / cm 3 is preferably 0.02 ⁇ ′cm or less, more preferably 0.001-0.010 ⁇ ′cm. If the powder resistance value exceeds 0.02 Q-C m, it becomes difficult to form a good conductive path when blended in a matrix such as resin.
  • the carbon fiber structure used in the present invention has high strength and conductivity, it is desirable that there are few defects in the graph end sheet constituting the carbon fiber. Specifically, for example, I measured by Raman spectroscopy
  • the carbon fiber structure according to the present invention preferably has a combustion start temperature in air of 750 ° C or higher, more preferably 800 to 900 ° C. As described above, since the carbon fiber structure has few defects and the carbon fiber has an intended outer diameter, the carbon fiber structure has such a high thermal stability.
  • the carbon fiber structure having the desired shape as described above is not particularly limited, and can be prepared, for example, as follows.
  • an organic compound such as a hydrocarbon is chemically pyrolyzed by a CVD method using ultrafine transition metal particles as a catalyst to obtain a fiber structure (hereinafter referred to as an intermediate), which is further subjected to a high-temperature heat treatment.
  • the raw material organic compound hydrocarbons such as benzene, toluene and xylene, alcohols such as carbon monoxide (CO) and ethanol can be used.
  • hydrocarbons such as benzene, toluene and xylene
  • alcohols such as carbon monoxide (CO) and ethanol
  • CO carbon monoxide
  • the “at least two or more carbon compounds” described in the above does not necessarily mean that two or more kinds of raw material organic compounds are used, but even if one kind of raw material organic compound is used.
  • a reaction such as hydrodealkylation of toluene and xylene occurs, and in the subsequent thermal decomposition reaction system, two decomposition temperatures are different.
  • a carbon compound is also included.
  • the decomposition temperature of each carbon compound is not limited to the type of carbon compound. Therefore, by adjusting the composition ratio of two or more carbon compounds in the raw material gas, a relatively large number of combinations are used as the carbon compounds. be able to.
  • alkanes or cycloalkanes such as methane, ethane, propanes, butanes, pentanes, hexanes, heptanes, cyclopropane, cyclohexane, etc., especially alkanes having about 1 to 7 carbon atoms; ethylene, propylene, butylene Alkenes such as alkenes, pentenes, heptenes, cyclopentene, etc., especially alkenes having about 1 to 7 carbon atoms; alkynes such as acetylene and propyne, especially alkynes having about 1 to 7 carbon atoms; benzene, tonylene, styrene, Aromatic or heteroaromatic hydrocarbons such as xylene, naphthalene, methenolenaphthalene, indene, and phenanthrene, especially aromatic or heteroaromatic hydrocarbons having about 6 to 18 carbon atoms, alcohols such
  • the carbon fiber structure according to the present invention can be produced efficiently by optimizing the mixing ratio by using the combination and adjusting the residence time in a predetermined temperature range or Z. Can do.
  • the molar ratio of methane / benzene is> 1 to 600, more preferably 1.1 to 200, More preferably, it is 3 to: L00.
  • This value is the gas composition ratio at the entrance of the reactor.
  • toluene is used as one of the carbon sources. In this case, considering that 100% of toluene is decomposed in the reactor and methane and benzene are produced at a ratio of 1: 1, the shortage of methane may be supplied separately.
  • methane to be added to toluene is not limited to the method of preparing fresh methane separately, but unreacted methane contained in the exhaust gas discharged from the reactor is circulated and used. It is also possible to use it.
  • composition ratio within such a range, it is possible to obtain a carbon fiber structure having a structure in which both the carbon fiber portion and the granular portion are sufficiently developed.
  • an inert gas such as argon, helium, xenon, or hydrogen can be used.
  • a mixture of a transition metal such as iron, cobalt, and molybdenum, or a transition metal compound such as pheucene and metal acetate, and a sulfur compound such as sulfur, thiophene, or iron sulfide is used.
  • the synthesis of the intermediate is performed by using a commonly used CVD method such as hydrocarbon, evaporating the mixture of hydrocarbon and catalyst as raw materials, and introducing hydrogen gas or the like into the reactor as a carrier gas. And pyrolyze at a temperature of 800-1300 ° C.
  • a plurality of carbon fiber structures having a sparse three-dimensional structure in which the fibers having an outer diameter of 15 to: LOOnm are joined together by granular materials grown using the catalyst particles as nuclei. Synthesize an aggregate from cm to several tens of centimeters.
  • the thermal decomposition reaction of the hydrocarbon as a raw material is mainly produced on the surface of granular particles which are grown using the catalyst particles as a nucleus, and the recrystallization of carbon generated by the decomposition is caused by the catalyst particles or granular materials. By proceeding in a certain direction, it grows in a fibrous form.
  • the tolerance between the thermal decomposition rate and the growth rate is intentionally changed, for example, as described above, the decomposition temperature as a carbon source.
  • the carbon material is grown three-dimensionally around the granular material that does not grow the carbon material only in one-dimensional direction.
  • the growth of such three-dimensional carbon fibers is not dependent only on the balance between the pyrolysis rate and the growth rate, but the crystal surface selectivity of the catalyst particles, the residence time in the reactor.
  • the temperature distribution in the furnace is also affected, and the balance between the pyrolysis reaction and the growth rate depends not only on the type of carbon source as described above but also on the reaction temperature and gas temperature.
  • the growth rate is faster than the pyrolysis rate as described above, the carbon material grows in a fibrous form, whereas if the pyrolysis rate is faster than the growth rate, the carbon material becomes Grows in the circumferential direction of the catalyst particles.
  • the growth direction of the carbon material as described above is made to be a multi-direction under control without making the growth direction constant.
  • Such a three-dimensional structure can be formed.
  • the composition of the catalyst, the residence time in the reaction furnace, the reaction temperature, and the gas It is desirable to optimize the temperature and the like.
  • a reactor other than the above-described approach using two or more carbon compounds having different decomposition temperatures at an optimum mixing ratio is used.
  • One approach is to generate turbulent flow in the vicinity of the supply port of the source gas supplied to the tank.
  • the turbulent flow here is a turbulent flow that is a vortex and a flow that rushes.
  • metal catalyst fine particles are formed by decomposition of the transition metal compound as a catalyst in the raw material mixed gas immediately after the raw material gas is introduced into the reaction furnace from the supply port. This is brought about through the following steps. That is, the transition metal compound is first decomposed into metal atoms, and then, cluster formation occurs by collision of a plurality of, for example, about 100 atoms. At the stage of this generated cluster, it does not act as a catalyst for fine carbon fibers, and the generated clusters further gather together by collision, resulting in about 3 ⁇ ! It grows to crystalline particles of about lOnm and is used as metal catalyst fine particles for the production of fine carbon fibers.
  • each metal catalyst fine particle of the aggregate is radially formed as a nucleus.
  • the thermal decomposition rate of some of the carbon compounds is faster than the growth rate of the carbon material as described above, the carbon material also grows in the circumferential direction of the catalyst particles, A granular portion is formed around the aggregate to efficiently form a carbon fiber structure having an intended three-dimensional structure.
  • the aggregate of metal catalyst fine particles may include catalyst fine particles that are less active than other catalyst fine particles or that have been deactivated during the reaction.
  • This carbon material layer is considered to form the granular part of the carbon fiber structure according to the present invention by being present at the peripheral position of the aggregate.
  • the specific means for generating a turbulent flow in the raw material gas flow is not particularly limited. It is possible to adopt a means such as providing some kind of collision part at a position where it can interfere with the flow of the raw material gas led out to.
  • the shape of the collision part is not limited in any way as long as a sufficient turbulent flow is formed in the reactor by the vortex generated from the collision part. For example, various shapes of baffle plates If one or more paddles, taper tubes, umbrellas, etc. are used alone or in combination, a plurality of forms can be adopted.
  • the intermediate obtained by heating the catalyst and hydrocarbon mixed gas at a constant temperature in the range of 800 to 1300 ° C is pasted with a patch-like sheet piece that also contains carbon nuclear power. It has a combined (incomplete, burnt-in) structure, and when it is analyzed by Raman spectroscopy, there are many defects that are very large. Further, the produced intermediate contains unreacted raw materials, non-fibrous carbides, tar content and catalytic metal.
  • high-temperature heat treatment at 2400 to 3000 ° C is performed by an appropriate method. That is, for example, this intermediate is heated at 800 to 1200 ° C to remove volatile components such as unreacted raw materials and tars, and then annealed at a high temperature of 2400 to 3000 ° C. At the same time, the catalyst metal contained in the fibers is removed by evaporation. At this time, in order to protect the material structure, a reducing gas or a trace amount of carbon monoxide or carbon dioxide may be added to the inert gas atmosphere.
  • the intermediate is annealed at a temperature in the range of 2400 to 3000 ° C, the patch-like sheet pieces made of carbon atoms are bonded together to form a plurality of graph-en-sheet-like layers.
  • a carbon fiber structure having a desired circle-equivalent mean diameter is obtained through a process of pulverizing into LOO m.
  • annealing is further performed in a state where the bulk density is low (a state in which fibers are stretched as much as possible and a porosity is large). Effective for imparting conductivity to fat.
  • the fine carbon fiber structure used in the present invention comprises:
  • the conductive sheet according to the present invention is a force obtained by blending the fine carbon fiber structure as described above in a polymer matrix.
  • the polymer matrix used in the present invention As such, various thermoplastic resins, thermosetting resins, natural or synthetic rubbers, and elastomers can be used depending on the application.
  • polypropylene polyethylene, polyethylene oxide, polypropylene oxide, polystyrene, polychlorinated butyl, polyacetal, polyethylene terephthalate, polycarbonate, polybutylacetate, polyamide, polyamideimide, polyetherimide, and the like.
  • thermoplastic resins such as oil, unsaturated polyester resin, furan resin, imide resin, urethane resin, melamine resin, silicone resin and urea resin, natural rubber, styrene butadiene rubber (SBR) ), Butadiene rubber (BR), isoprene rubber (IR), ethylene 'propylene rubber (EPD M), nitrile rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), urethane rubber, silicone rubber, fluoro rubber, acrylic rubber (ACM) , Epoxychlorohydrin rubber, Ethyleneacrylic rubber, Norbornene rubber and other plastic elastomers such as styrene
  • the conductive sheet according to the present invention does not destroy the structure by applying excessive shear stress to the fine carbon fiber structure when mixing the polymer matrix component and the fine carbon fiber as described above.
  • the above-described carbon fiber structure can be blended with a polymer matrix component, melt-kneaded to disperse the carbon fiber in the matrix, and then produced by extrusion, vacuum forming, pressure forming, etc.
  • a carbon fiber structure as described above is added to a polymer solution or dispersion in which a polymer matrix component is dissolved and dispersed using an appropriate organic solvent or the like, and a media mill such as a ball mill is added. From a coating method of forming a film by dispersing using a suitable stirring or dispersing apparatus and then spreading on a suitable substrate and then removing the solvent! Can be manufactured.
  • the liquid used as a solvent or a dispersion medium is particularly Although not limited, it is possible to select an appropriate one depending on the used fat component. Specifically, for example, water; methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, aryl Alcohols such as alcohol; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethanolo ether, polypropylene glycol monoethyl ether ether, polyethylene glycol monovinyl ether, polypropylene glycol monoallyl ether, etc.
  • water methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, aryl Alcohols such as alcohol; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethanolo ether, polypropylene glycol monoethyl ether ether, polyethylene glycol monovinyl ether,
  • Glycol or its derivatives glycerol, glycerol and its derivatives such as glycerol, glycerol monoethyl ether, glycerol monoallyl ether; N-methyl Amides such as loridone; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; liquid paraffin, decane, decene, methyl naphthalene, decalin, kerosene, diphenol methane, toluene, di Methylbenzene, ethynolebenzene, jetylbenzene, propylbenzene, cyclohexane, hydrocarbons such as triphenyl with partial addition of water, polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially-phenyl substituted Silicon
  • the conductive sheet of the present invention contains an effective amount of the above-described carbon fiber structure together with the polymer matrix component as described above.
  • the amount varies depending on the use of the conductive sheet, the type of the polymer matrix component, and the like. If it is less than 01%, the electric conductivity in the formed film may not be sufficient. On the other hand, if it exceeds 30.0%, the mechanical strength, flexibility and the like of the sheet formed in reverse may be lowered.
  • the conductive sheet of the present invention even if the amount of the carbon fiber structure as the filler is relatively low, fine carbon fibers can be arranged in the matrix with a uniform spread. As described above, a conductive sheet having excellent electrical conductivity can be formed.
  • the conductive sheet according to the present invention in addition to the carbon fiber structure, various known additives, for example, a filler, a reinforcing agent, various stabilizers, an oxidation agent, and the like within a range that does not hinder its purpose. Inhibitors, ultraviolet absorbers, flame retardants, lubricants, plasticizers, solvents, and the like can be blended.
  • the conductive sheet according to the present invention has one or both sides thereof in addition to the layer containing the carbon fiber structure as described above in the polymer matrix, depending on the use or the like.
  • various functional layers such as a base material layer and an insulating protective layer may be provided to form a multilayer structure.
  • Such a multilayer structure is formed, for example, by coextrusion at the time of melt extrusion, or by further coating on this layer after forming a layer comprising a carbon fiber structure in a polymer matrix. It is possible.
  • the film thickness of the conductive sheet according to the present invention is not particularly limited, but the film thickness is 1.0 to: LOOO. O ⁇ m, more preferably 5.0 to 300. O / zm is preferable. If the film thickness is less than 1. O / zm, film-like defects such as pinholes may occur, and uniform conductive properties may not be imparted. On the other hand, the film thickness exceeds 1000. O / zm. However, the conductivity characteristics cannot be expected to be improved as compared with those having a thickness smaller than that, and there is a possibility that problems such as a decrease in film strength may occur.
  • the conductive coating film formed by the conductive sheet according to the present invention is not particularly limited, but typically has a surface resistance value of 10 12 ⁇ / « ⁇ 2 or less, particularly 10 2 -10 1 Q Q / cm 2
  • the use of the conductive sheet according to the present invention is not particularly limited.
  • electrode materials such as separators for various secondary batteries, separators for fuel cells, electrodes for electric double layer capacitors, Sheets for packaging electronic parts, various antistatic materials in electronic copiers or electronic printers using the electrostatic latent image developing system, and other various wiring, electrode members, antistatic sheets, etc. It is.
  • TG-DTA Mac Science TG-DTA
  • the temperature was increased at a rate of 10 ° CZ while flowing air at a flow rate of 0.1 liters Z, and the combustion behavior was measured.
  • TG shows a weight loss
  • DTA shows an exothermic peak, so the top position of the exothermic peak was defined as the combustion start temperature.
  • the carbon fiber structure after annealing was examined using a powder X-ray diffractometer CiDX3532, manufactured by JEOL Ltd.). ⁇ ⁇ -rays generated at 40 kV and 30 mA in a Cu tube are used, and the surface spacing is measured in accordance with the Gakushin method (latest carbon materials experimental technology (analysis and analysis), carbon materials society edition). Was used as an internal standard.
  • CNT powder lg is weighed and made of resin grease (inner dimensions L 40mm, W 10mm, H 80mm) Fill and compress to read displacement and load.
  • resin grease inner dimensions L 40mm, W 10mm, H 80mm
  • the voltage at that time was measured, and when the density was measured to 0.9 gZcm 3 , the pressure was released and the density after restoration was measured.
  • the resistance when compressed to 0.5, 0.8 and 0.9 g / cm 3 shall be measured.
  • the particle part which is a bonding point between carbon fibers, is regarded as one particle, and its outline is image analysis software WinRoof (trade name, Mitani Corp.
  • the area within the contour was obtained, and the equivalent circle diameter of each granular part was calculated and averaged to obtain the average particle diameter of the granular part.
  • the circularity (R) is calculated based on the following equation from the area (A) in the contour measured using the image analysis software and the measured contour length (L) of each granular portion. The degree was obtained and averaged.
  • the outer diameter of the fine carbon fiber in each of the targeted carbon fiber structures is obtained, and from this and the equivalent circle diameter of the granular part of each carbon fiber structure, the granular part in each carbon fiber structure was determined as a ratio to the fine carbon fiber and averaged.
  • the granular portions are connected by fine carbon fibers.
  • the distance between adjacent granular parts connected by fine carbon fibers in this way (the center force of the granular material at one end and the length of the fine carbon fiber including the central part of the granular material at the other end ) Were measured and averaged.
  • a carbon fiber structure was added to 100 ml of toluene placed in a vial with a lid at a rate of 30 gZml to prepare a dispersion sample of the carbon fiber structure.
  • an ultrasonic cleaner having a transmission frequency of 38 kHz and an output of 150 w (trade name: USK-3, manufactured by SENUDY Co., Ltd.) Ultrasonic waves were irradiated, and changes in the carbon fiber structure in the dispersion sample were observed over time.
  • the 50 50 average diameter was determined in the same manner as described above.
  • the calculated D average length of fine carbon fibers is about half of the initial average fiber length.
  • the D average diameter of the granular portion at the time was compared with the initial average diameter, and the fluctuation ratio (%) was examined.
  • a carbon fiber structure was synthesized using toluene as a raw material by the CVD method.
  • the catalyst was a mixture of Huekousen and Thiophene, and the reaction was carried out in a hydrogen gas reducing atmosphere. Toluene and catalyst were heated together with hydrogen gas to 380 ° C, supplied to the production furnace, and pyrolyzed at 1250 ° C to obtain a carbon fiber structure (first intermediate).
  • Fig. 8 shows a schematic configuration of a generating furnace used in manufacturing the carbon fiber structure (first intermediate).
  • the production furnace 1 has a power having an introduction nozzle 2 for introducing a raw material mixed gas composed of toluene, a catalyst and hydrogen gas as described above into the production furnace 1 at the upper end thereof.
  • a cylindrical collision portion 3 is provided outside the introduction nozzle 2. The collision part 3 can interfere with the flow of the raw material gas introduced into the reactor through the raw material gas supply port 4 located at the lower end of the introduction nozzle 2.
  • the inner diameter a of the introduction nozzle 2, the inner diameter b of the production furnace 1, the inner diameter c of the cylindrical collision part 3, and the raw material mixed gas from the upper end of the production furnace 1 Each dimension is defined as follows: distance d to inlet 4; distance e from raw material mixed gas inlet 4 to the lower end of collision section 3; and f from raw material mixed gas inlet 4 to the lower end of generation furnace 1.
  • the feed gas introduction rate into the reactor was 1850 NLZmin and the pressure was 1.03 atm.
  • this second intermediate was heat treated at 2600 ° C in argon at a high temperature, and the resulting carbon fiber was obtained.
  • the aggregate of structures was pulverized with an airflow pulverizer to obtain a carbon fiber structure used in the present invention.
  • Fig. 3, Fig. 4A and Fig. 4B show SEM and TEM photographs observed after the obtained carbon fiber structure was dispersed in toluene with ultrasonic waves and an electron microscope sample was prepared.
  • FIG. 5 shows an SEM photograph of the obtained carbon fiber structure placed on an electron microscope sample holder as it is, and Table 1 shows the particle size distribution.
  • the obtained carbon fiber structure had a circle-equivalent mean diameter of 72.8 m, a bulk density of 0.003 2 g / cm 3 , a Raman ID / IG ratio value of 0.090, and a TG combustion temperature of 786 ° C, spacing is 3. 383 angstroms, powder resistance is 0.0084 ⁇ 'cm, and density after restoration is 0.25 gZcm 3 .
  • the average particle size of the granular portion in the carbon fiber structure was 443 nm (SD207 nm), which was 7.38 times the outer diameter of the fine carbon fiber in the carbon fiber structure.
  • the circularity of the granular part was 0.67 (SD 0.14) on average.
  • the average fiber length (D) of 6.7 m is almost half of 6.7 m.
  • the average diameter (D) of the granular part 500 minutes after application of ultrasonic waves was compared with the initial initial average diameter (D) 30 minutes after application of ultrasonic waves.
  • Fine carbon fibers are synthesized by CVD using a part of the exhaust gas from the generator furnace as a circulating gas and using a carbon compound such as methane contained in this circulating gas as a carbon source together with fresh toluene. did.
  • the synthesis was carried out in a reducing atmosphere of hydrogen gas, using a mixture of pheocene and thiophene as a catalyst.
  • fresh raw material gas toluene and catalyst were heated to 380 ° C in a preheating furnace together with hydrogen gas.
  • a part of the exhaust gas taken out from the lower end of the production furnace is used as a circulating gas, and its temperature is adjusted to 380 ° C. Supplied.
  • composition ratio in the circulating gas used was CH 7.5% in terms of volume-based molar ratio, C
  • the final raw material gas is contained in the mixed circulating gas, and C H, C
  • the amount was very small and practically negligible as a carbon source.
  • the first intermediate synthesized as described above was calcined at 900 ° C in argon to separate hydrocarbons such as tar and obtain a second intermediate.
  • the R value was 0.83.
  • the SEM and TEM photographs were almost the same as those in Synthesis Example 1 shown in FIGS.
  • this second intermediate was heat-treated at 2600 ° C in argon at a high temperature, and the resulting carbon fiber structure aggregate was pulverized with an airflow pulverizer to obtain the carbon fiber structure according to the present invention. It was.
  • the obtained carbon fiber structure had a circle-equivalent mean diameter of 75.8 m, a bulk density of 0.004 g / cm 3 , a Raman I / 1 ratio of 0.086, and a TG combustion temperature of 807 ° C, spacing is 3.386 on
  • the dust resistance and the powder resistance value were 0.0075 ⁇ -cm, and the density after restoration was 0.26 gZcm 3 .
  • the average particle size of the granular portion in the carbon fiber structure is 349.5 nm (SD180. In m), which is 5.8 times the outer diameter of the fine carbon fiber in the carbon fiber structure. It was. The circularity of the granular part was 0.69 (SD 0.15) on average.
  • the average fiber length (D) of 6.3 m is almost half the length of 6.3 m.
  • the average diameter (D) of the granular part 500 minutes after application of ultrasonic waves was compared with the initial initial average diameter (D) 30 minutes after application of ultrasonic waves.
  • a compound was produced in the same manner as in Example 1 except that the carbon fiber structure obtained in Synthesis Example 2 was used, and subjected to the same test. As a result, the surface resistance is 8.1 ⁇ 10 2 ⁇ / « ⁇ 2 .
  • Carbon fiber structure obtained in Synthesis Example 1 above was added to 100 parts by mass of polypropylene (Idemitsu Kosan J-466HP) resin at a ratio of 1.5 parts by mass, and kneaded using a twin screw extruder.
  • the thermoplastic fiber was supplied from the hopper of the twin screw extruder, and the carbon fiber structure obtained in Synthesis Example 1 was weighed from the middle of the extruder in the melted state. Feeded by a feeder.
  • a sheet having a film thickness of 10.0 m was prepared by extrusion stretch molding, and the surface resistance value was evaluated. As a result, the surface resistance value was 9.4 ⁇ 10 2 ⁇ « ⁇ 2 .
  • the obtained sheet There was no unevenness on the surface, and the film thickness was uniform throughout.

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Abstract

La présente invention a trait à une feuille conductrice d'électricité comportant une structure de fibres de carbone dans une matrice polymère en une proportion de 0,01 à 30 % en poids par rapport à la quantité totale de la feuille, ladite structure de fibres de carbone présentant une structure de réseau tridimensionnel formé par des fibres de carbone ayant un diamètre extérieur de 15 à 100 nm et ayant une partie particulaire qui lie les fibres de carbone de sorte que les fibres de carbone s'étendent depuis la partie particulaire, et la partie particulaire étant formée pendant le procédé de croissance des fibres de carbone. La feuille conductrice d'électricité peut présenter une bonne tenue de film et une conductivité élevée.
PCT/JP2006/321122 2005-10-25 2006-10-24 Feuille conductrice d'electricite WO2007049590A1 (fr)

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EP1950768A1 (fr) 2008-07-30
CN101297378A (zh) 2008-10-29
KR20080052678A (ko) 2008-06-11
JP2007122927A (ja) 2007-05-17
EP1950768A4 (fr) 2009-11-25
US20090263642A1 (en) 2009-10-22

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